Mercaptan oxidation process



JHM 3, 194.7. w. w. cRouc|-| ERCAPTAN OXIDATION PROCESS v Filed nay 1:5. 1944 cRoucH INVENTOR wi w MAM Patenten June 3 1947 MERCAPTAN OXIDATION PROCESS VWillie W. Crouch, Bartlesville, Okla., assigner to` Phillips` Petroleum Company, a corporation of Delaware l i Application May 13, 1944, serialize. 535,504

(c1. zee-sos) Claims.

This invention relates to a'ncvel and improved process for the conversion of mercaptans having high molecular weights tothe corresponding disulfides. More speciiically, theA present invention relates to the oxidation of aliphatic mercaptans having high molecular weights by the novel combination of cupric chloride and hydrogen peroxide as the oxidizing agents in two separate `treatments.

Mercaptans can be converted to disulildes under the influence of a variety of mild oxidizing agents.

This conversion or oxidation is of special interest in the so-called sweeteningof petroleum distil lates. Copper halides have been widely employed as oxidizing agents in such processes.l The following equations represent reactions lwhich are postulated to take place inconventionalcoppersweetening processes for converting mercaptans to disulfides: (1) 4rRf--SH-i-2CuClz- V In the foregoing equations R represents an aliphatic hydrocarbon radical.` The first equation represents the conversion of a mercaptan to a disulfide and a cuprous mercaptide and the second equation represents the conversion ofthe cuprous mei'captide formed in the first reaction to a disulfide. The `cuprous chloride formed in the second reaction is continuously oxidized in the third reaction tothe cupric form by oxygen or air dissolved in the hydrocarbon. Coppersweetening processes thus involve very `little if any consumption of chemicals other than oxygen. In the production of disulfldes having high molecular weights, that are suitable for use as .oxidized with cupric chloride solution, even at elevated temperatures orwhen present in dilute solutions in hydrocarbons, the oxidation isnot completed within a reasonably short period and the product is contaminated with substantial promercaptans of low molecular weight, such as` ethyl mercaptan and butyl mercaptan, are treated in accordance with conventional copper-sweetening processes that are used for the treatment of gasoline and low-boiling petroleum distillates.

An object of this invention is to provide a process for the conversion ol.' alkyl mercaptans and mixtures of alkyl mercapta'ns having a molecular weight or an average molecular weight within the range of approximately 174 to approximately 258 (Cinto Cie mercaptans) or higher to the corresponding alkyl disuldes.

Another object `of the present invention is to provide a process for the oxidation of such highmolecular-Weight tertiary mercaptans or mixtures containing them to the corresponding disulfldes by means of a related sequence of operations `employing a combination of oxidizing agents, namely, cupric chloride solution and hydrogen peroxide solution.

An additional object of the invention is the provision of a continuous oxidation process for the conversion of high-molecular-weight mercaptans to disulfides in which aminimum consumption of chemicals is involved. l I

Further objects and advantages of the invention., some `of which are referred tospecically hereinafter, will `be ,apparent to thoseskilled in the art to which the invention pertains.v

In copending application Seriahlo. 511,432, filed November 23, 1943, a process is" described in which the inherent disadvantages of oxidation with cupric chloride are obviated by carrying out the oxidation in the presence of a solution containing both cupric chloride andY hydrogen perox- V ide. Although neither of said oxidizing agents alone capable of effecting the desired conversion, when used simultaneously and in combination the conversion may be effected to provide a satisfactory'product. Such a treatment,V however, involves a consumption of relatively large t proportions of hydrogen peroxide.'

I have discovered that, by the use of arnovel related sequence of operations as hereinafter set forth. the consumption of hydrogen peroxide in in the second treatment by both cupric chloride while the morev refractory components may be p converted in a, subsequent operation in the pres-A ence of hydrogen peroxide and hydrochloric or other acid. In this manner the hydrogen peroxide consumed in the reaction yis reduced to substantially only that amount necessary to convert anyrefractory mercaptans and any unconverted cuprous mercaptides that remain after the treatment with cupric chloride. which is converted in the rlrst treatment to cuprous chloride may be regenerated to cupric chloride ,by oxidation with air.

In accordance with the process .of the present invention, the mercaptan or mixture of mer-- captans having high molecular weights is treated with a cupric chloride solution containing a high concentration of chloride ions. The chloride ions are present to maintain in solution any cuprous chloridethat is formed in the Atreatment. The success of this first treatment depends on the maintenance of a high oxidation potential inthe cupric ychloride solution, whichin turn is dependent on maintenance of a high ratioof cupri'c to cuprous ions. Therefore, in the first treatment a short contact time is provided and recirculation of the non-aqueous phase and of the'regenerated cupric chloride phase are employed. The actual conversion per pass is so regulated that the cupric chloride solution is regenerated after each pass by simple aeration or treatment with oxygen. When the maximum desired conversion of mercaptan to disuliide has been reached in this treatment with cupric chloride, the effluent containing any unconverted mercaptan, cuprous mercaptide and all the disulfide is charged to a second reactor to undergo a second treatment in which it is contacted with or subjected to the action of controlled proportions of hydrogen peroxide. This second treatment is conducted in the presence of regenerated cupric chloride solution, which is used for providing hydrochloric acid, but may be conducted lin its absence if suicient hydrochloric acid is added or is presentin the hydrogen peroxide or non-aqueous phase. The conversion of cuprous mercaptide in the second treatment probably takes place according to the following equation 1. v

The hydrochloric acid in this reaction may be furnished by the regenerated cupric chloride solution which contains an excess of this reagent by virtue of the reaction represented by Equation 1 hereinbefore.

Any mercaptan that has notbeen converted to a, cuprous mercaptide'in the :first treatment or any refractory mercaptan that has not been affected by the rst treatment may be converted in the second treatment to a cuprous mercaptide by the action of cupric chloride, which is formed in said treatment from the action of hydrogen peroxide on cuprous mercaptide already present The cupric chloride in the material in accordance with Equation 4. Or the mercaptan may be converted to disulfide and hydrogen peroxide in conjunction, or from the hydrogen peroxide alone, perhaps in accordance with a reaction similar to that expressed in the following equation:

In the iirst treatment with'cupric chloride, part or the-greater portion of the mercaptan may be converted to cupric mercaptide, in accordance with Reaction l hereinbefore, and lnone or a substantial-portion of the copper mercaptide thus formed may be converted to the corresponding disulde in accordance with Reaction 2 hereinbefore. However, there may be mercaptans i present in certain mixtures which are refractory or are not affected by' the treatment with cupric chloride.

The conversion of these refractory mercaptans and cuprous mercaptides which are present in the efiiuent of the first treatment is effected in the second treatment with hydrogen peroxide.

Cupric chloride is formed in this second treatment from the cuprous mercaptide, probably in accordance with, the reaction expressed in Equation 4. This reactionrequires hydrochloric acid, which is preferably supplied by circulation of the cupric chloride solution to the reaction mixture, although it may be supplied by other means and removed from the system by conventional methods. Cupric chloride which is present in this second treatment, which results from the conversion of cuprous mercaptides to disuliides or is present in any cupric chloride solution circulated thereto, may react in conjunction with thehydrogen peroxide to convert the refractory mercaptans directly to `disulfidesr or to cuprous mercaptides and thence to disulfides. The amount of hydrogen peroxide-,which is used in the second treatment is controlled so asv to effect only the desired conversion or convcrsionsand will be dependent upon the extent to which the conversions have proceeded in the iirst treatment.

While the vforegoing general description may be construed to be related only to batch or stepwise operation, continuous operation is also and 1 more particularly contemplated, in which the first and second treatments proceed simultaneously or concurrently on different portions of the mixture undergoing treatment with continuous flow of cupric chloride solution from the aeration or regenerating zone to the iirst treatment, and with a flow of cupric vchloride formed in the'second treatment to the first treatment, thereby resulting in virtually no depletion in copper content nor any substantial change in oxidation potential. A flow of regenerated cupric chloride solution to the second treatment, is also contemplated for the purpose of providing the hydrochloric acid required therein.

The advantage of the process ofthe present in- I vention is manifest in the reduction in the quantity of hydrogen peroxide which is used. Whereas substantially the same conversion can be accomplished in a single treatment, as described in the vhereinbefore mentioned co-pending application Serial No. 511,432, hydrogen peroxide slightly in excess of the theoretical quantity for the mercaptan-disulde conversion must be ern-y ployed in order to insure the production of a product free from mercaptans and copper. By

utilizing air or oxygen'forthe regeneration of the cupric chloride solution, asin the present process, a considerable reduction inthe amount of hydrogen peroxide consumed and in processing` costs is realized, since in most cases` not more than 20 per cent ofthe quantity of hydrogenper` oxide used inthe processv of said copending ap-v plication is required. f

A specific preferred embodiment of my invention is illustrated in the accompanying drawing which consists of a simplified process flow dlagram. The mercaptan charge or feed, whichV comprises a` mixture `of substantially tertiary mercaptanshaving an average molecular weight` of about 210, is withdrawn` from storage tanky I* and charged to reactor 3. Simultaneously the oxidizing agent comprising aqueous cupric chlo-y ride solution is injected.intothereactor from storage tank I3 via line` I4. Thereactor may be of conventional design, the requirements -being resistance to-cupric ion corrosion and means forv maintenance of an intimate dispersion of, Centrifugal vided with internal coils for purposes of temperature control. f

After a suitable contact periodlfor partial oxi-Y dation of the mercaptan, the emulsion is discharged from reactor 3 through line liinto sepae rator 5 where a liquid interface is maintainedbe.. tween the aqueous and non-aqueous phases.A The partially spent cupric chloride solution isl continuously withdrawn through line 8 land thence discharged into a regenerating zone 9. Air or other oxygen-rich gas is introduced into regenerating zone 9 through line I to convert cuprous salt to the cupric salt. The oxidizing gas is preferably presaturated with water` to offset any evaporation effectsiwhich might occur during the regeneration. ,I'he regenerated solution continuously flows into line Il,V from which a portion is* pumped to reactor lII through line I2,iwhi1e the i remainder is returned to storage tank I3. Regeni erated cupric chloride solution is chargedv to re-` actor I'I rather than unregenerated solutionsince unregenerated solution would' consume hydrogen peroxide and thereby not afford the most advani tageous benefits of this process.y `The function of the cupric chloride solution in` reactorll is to supply hydrochloric acid, but it may `be `dispensed with if acid is added instead. i i.

The non-aqueous layer in tank 5, `which comprises any unconverted mercaptamalkyl disul-H des and cuprous mercaptide, is drawn on into line 6, from which some or a substantial portion is recycledvia line 'l to feed line 2 foriadditional treatment, While the remainder is discharged into reactor I'l for the second treatment with hydrogen peroxide. and line I6 and ,regenerated cupric chloride solution from line VI2. arecharged tothe reactor I1 i along with the product stream from line 6. In reactor Il, which may be similar in design to reactor 3, the cuprous mercaptides are converted to di'suldesby the action of the peroxide orby the combined` action of hydrogen peroxide and cupric ions, which also willconvert .unchanged mercaptan to the corresponding disulfide.

Hydrogen peroxide from tank l5 i through line `2li to product storage tank 2|. The diluted aqueous layer is discharged `through line,r 22 into an evaporating zone 23 where excess water introduced with thehydrogen peroxide is re-V moved through line 24. The concentrated cupric chloride'solution is continuously pumped from the evaporation zone 23 by means of line 25 and line Il to 'storage tank I3.

'I'he oxidizing copper solution` which is used in this process consists of an aqueous solutioniof cupriccopper,in thepresence of a chloride yion concentration equivalent to that of a 10 to 20 per cent sodium chloride solution. Sulfate ions may be present in the solution. The cupric copper 'concentrationlmay vary from approximately 3 to approximately 14 per cent by weight. al-V though intermediate concentrations of from approximately 5to 4approximately 10 per cent are` preferred. Cupricwsulfate crystals maybe used for preparing a cupric chloride solution, as dei scribed hereinafter in Example 1.

- a temperaturewithin the range of approximately Thel eilluent emulsion fromreactor Il is conducted through line I8 to` separator I9, from i which the alkyl disulfide product is withdrawn below 360 m'illivolts.

The hydrogen peroxide of the present oxidizing system may be an aqueouscommercial stabilized solution having` a concentration from approxi-` mately `3 to approximately 30 per cent by weight of hydrogenperoxide (10 to 100 volumes of oxygen). The more concentrated solutionscontaining from approximately 15 to approximately 30 per cent hydrogen peroxide are preferred. Such commercial hydrogen peroxide solutions mayv containsmallproportions of hydrochloric acid Y and acetanilide or other stabilizers, e

In the preferred continuous operation of the process of thisinvention, the .volume ratio of cupric chloride solution tonon-aqueous phase, the recycle to fresh feedvolume ratio and the reaction or contact time are variables that are i adjusted to obtain optimum performance from the cupric chloride .oxidizing solution. Under the preferred operating temperatures and `concentrations of cupricchloride solution, an oxidation potential within the rangeof approximately l115 to approximately 360 millivolts, as developed inI the copper solution betweena polished platinum i i or gold electrode anda saturated. calomel half cell, is ordinarily satisfactory.` ,The measurementof this oxidation potential is employed in establishing the `operating ranges of the aforementioned variables. Since the oxidation potential increases with temperature, it is preferred to carry out both stages of oxidation at to approximately 150i. F. v

In order to maintain a high oxidation potential the contact time in the yrst reactor is so adjusted that oVer-rcactiondoes not occur in any onepass through the vreaction zone. For most efficient operation of the cupric chloride solution regenerator, -not more than approximately 5 to approximately 6 per cent of the i copper should be in the cuprous state. Since an increase in the cupric-cuprous ion` ratio results in a decrease in oxidation potential, the con` tact time can be adjusted to give a conversion which does not reduce the potential substantially value within the range' of approximately `0.5 toV approximately liminutes, with values of from 1 to 5 minutes being preferred. y

To avoid the employment of excessive` volumes of cupric chloride solution, both the mercapt-an and cupric chloride solution-streams ofthe iirst treatment are recycled, with the latter being subjected to continuous regeneration -during the `Ordinarily the residence lor contact time inthe reactor is adjusted at a external portion of thev cycle. A volume ratio ofy aqueous to non-aqueous phase in the reactor is maintained between approximately 2 and approximately 10 .or higher. Although this ratio will be largely determined by the oxidationcharacteristics of the feed, with mosthigh-molecularweight mercaptans this ratio is held between approximately 8 and approximately, 10. The volume ratio of mercaptan recycle to fresh feed is usually maintained between approximately and approximately 10, in'erder'to realize maximum conversion in this stage,

In the-second reactor, conditions of temperature, contact time and volume ratio of aqueous to non-aqueous phases -are held at values approximately equal to those of the first reactor. Due to extensive recycling of eupric chloride solution in the rst treatment, it 'ismerely necessary `to maintain the same volume ratio of nonaqueous to aqueous 'phase in the second stage in order to have present suicient hydrochloric acid to eiect the conversion of cuprous mercaptide to disulfide represented inv Equation 4. Ordinarily no recirculation of the product stream is necessary in thisstep. The quantity of hydrogen peroxide will depend on the condition of the y effluent from the first treatment.v Quantitative chemical analytical determinations of the cuprous content and mercaptan content of the feed to the second treatment will serve to determine the quantity of hydrogen peroxide required. In the absence of results'of chemical analyses, the second treatment may be operated on the assumption that maximum hydrogen peroxide consumption will be required. From the equations, maximum hydrogen peroxide is equivalent to onehalf of the original mercaptan content. We have found that the addition of hydrogen peroxide, so calculated, results in an ample excess of oxidizing agent over that actually required for the production of a copper-free and substantially mercaptan-free product.

The following examples illustrate in greater de tail the operation of specic embodiments of this invention. Numerous modications will be apparent to those skilled in the art in accordance with the principles set forth herein.V

Example 1 y The oxidation of a mixture of high-molecularweight -mercaptans comprised predominantly of tertiary dodecyl mercaptans was accomplished in a two-stage batch process, involving treatment to be substantially free of mercaptans. Contamination of this material with cuprous' mercaptide was demonstrated by shaking a small portion of the crude product oil with potassium ferrocyanide solution, whereupona copious precipitate of cuprous ferrocyanidefornied.

Approximately g. of the-disulfide-cuprous mercaptide product obtained in this manner from the' foregoing cupri'c chloride oxidation was suspended in a dilute aqueous solution of hydrochloric acid by means of mechanical agitation. Ten grams of l5 per cent hydrogen peroxide solution was gradually added to the suspension while maintaining the temperature at 120 F. The clear aqueous solution rapidly developed the blue color of cupric ions. At the conclusion of the reaction, the oil layer was separated from the aqueous phase and washed with water; The absence of cuprous copper in the oil phase was established' by means 'of the potassium ferrocyanide test while the absence of residual mercaptan was confirmed by a negative test for acid `when an alcoholic solution of the oil phase was treated with `silver nitrate solution,

' Example 2 An additional 50 g. of the product from the first treatment with cupric chloride was suspended in the copper reagent recovered from the first treatment in Example l and the entire suspension was then 'treated with 15 per cent hydrogen peroxide. as described in Example 1. The product from this treatment, after separation and washing with water, was also found to be free of copper and mercaptans.

Instead of treating pure mercaptans or mixturesof mercaptans, such materials may be subjected to the process of the invention in diluted form as in solution in inert solvents such as petroleum distillates, which are not miscible with water. f

Although the foregoing speciflcationirefers particularly to alkyl mercaptans and disuldes, the `process of the invention is adaptable generally with cupric chloride solution in the first stage and hydrogen peroxide in the second stage,'as

follows: v

The oxidizing copper solution was prepared by dissolving 190 g. of copper sulfate pentahydrate and 173 g. of sodium chloride in 920 g. of water.

Approximately 480 g, of the above solution was charged to a glass reactor equipped with a stirrer. rI'he temperature of the copper oxidizing solution was maintained at 120 F, while the liquid mercaptan was charged theretoat a rate of Ogliquid cc. per hour. During the addition of the mercaptan, the copper solution was continuously withdrawn from the reactor for aeration in a separate vessel and then returnedl to the reactor. The copper solution gradually faded in color due to` the loss of copper to the product stream; however, ,no visible signs of cuprous chloride were evident.

The'water-insoluble oil was separated from the copper solution and was washed with water to give a pale yellow viscous liquid which was found to the treatment or conversion of mercaptans in general, particularly aliphatic mercaptans and more particularly, alkyl mercaptans, to corresponding disuldes. Y

Inasmuch as the foregoing specification comprises preferredrembodiments of my invention, it is to be understood that it is not limited thereto, and that alterations andmodification's may be'made-therein, in accordance with the principlesdescribed, to adapt the invention to other specific uses. The invention is not to be limited by any theories which have been proposed to account for the advantageous results obtained by the practice of the invention or to explain its operation but is to be limited only by the scope of the appended claims. I

I claim:

1. In a process for the oxidation of a high mo- I resulting product is' substantially free from iinoxidized mercaptans fand copper compounds.

2. In a process for the production of a disulde by treatment of'a high molecular weight alkyl mercaptan with cupric chloride and Vhydrogen peroxide, the improvement whereby the consumption of hydrogen peroxide issubstantially reduced and the cupric chloride is regenerated, which comprises subjecting the mercaptan tothe action of an aqueous solution of cupric chloride to eie'ct partial oxidation of a substantialproportion of the mercaptan, separating the aqueous phase containing hydrochloric acid land copper salts from the non-aqueous phase,` subjecting the aqueous phase to the action ofanoxygen-containing i gas to eiect substantial regeneration of the cupric chloride therein' using said aqueous phase` for further oxidation of mercaptans, and thereafter subjecting the non-aqueous phase to further treatment in the presence of hydrochloric acid an alkyl mercaptan having a hig`h`n'iolecularl weight with an aqueous solution of cupric chloride and thereafter treating` the resulting product in the presence of hydrochloric acid Withhydrogen peroxide in an amount suflicient to eifectV substantially complete oxidation of said mercaptan.

l 4. A process for the production of an aliphatic disulfide having a high molecular weight from a high molecular `weight alkyl mercaptan, which comprises subjecting an alkyl mercaptan `to `the action of a solution of cupric chloride in-liquid phase, to effect partial oxidation of asubstantial proportion of the mercaptan, and thereaftersubjecting the resulting partially oxidized product in the presence of hydrochloric acid to the action of hydrogen peroxide in an amount 4suiiicient to effect substantially complete oxidation and obtain a product substantially free' from unoxidized mercaptans and copper compounds.

5. A process for the production of an alkyl, disulde from an alkyl mercaptan having a molecular weight in excess of approximately 174, which comprises subjecting said mercaptanto the action of an aqueous solution of cupric'chloridein liquid phase until a substantial proportion of the mercaptan has been partially oxidized, and thereafter subjecting the resulting partially oxidized product in liquid phase in the presence ofhydrochloric acid to the action of an aqueous solution of hydrogen peroxide in such amount that a-prod uct which is substantially free from unoxidized mercaptans and copper compounds is obtained.

treatments with the cupric chloride solution and the hydrogen peroxide solution are conducted at temperatures Within the range of approximately 100 to approximately 150 F. y

7. A process for the production of a mixture of alkyl disuliides from a mixture of alkyl mercaptans having an average molecular'weight in 8. A process for the production Vof an alkyl disuliide'liaving" a high molecular Weight from an 'alkyl'mercaptan, which comprises `in a rst treatment subjecting an alkyl mercaptanhaving ar aqueous phase containinghydrochloric acid and l copper salts from the non-aqueous phase, subjecting the aqueous phase to treatment with an oxygen-containing gas to regenerate cupric chloride,

`Y subjecting .said non-aqueous phase in `the presence of a portion of the regenerated cupric .chloride solution' containing!` hydrochloric acidY in `a second treatment Vto the action of hydrogen peroxide in such amount and for such period that a product which is substantially free lfrom unoxidized mercaptans and copper compounds is obtained, separating the product of the second cupric ,chloride and subsequently using said aqueous phase together withjhe regenerated aqueous treatment `from the .aqueous phase containing phase of the, rstf treatment for conversion of further quantities 'ofimercaptans `9. A continuous process for the production of a mixture of alkyl disuldes having ahigh average .molecular weight from a Vmixture of alkyl mercaptans, which compriseslin a'first treatment continuously passing a mixture of alkyl mercaptans havingV an average molecular Weight within therangeof approximately 174 to approximately 258 into Contact with anaqueous` solution of cupric` chloride for a period suflicient to effect partial oxidation of a substantial proportion ofc the mercaptans, continuously separating the aqueous phasecontaining hydrochloric acid and l copper salts from the non-aqueous phase, con- 6. Aprocess as defined in claim 5 in which the' tinuously removing the aqueous phase and subjecting it to treatment with an oxygen-containj ing .gas tojregenerate cupric chloride, continuously passing said non-aqueous phase together witha stream comprising a portion of the regenerated cupric chloride solution containing hydrochloric acid in a second treatment into contact with hydrogen peroxide in such proportion and for such period that a product which is substantially free from unoxidized mercaptans and aqueous phase of the rst treatment into contact with the mixture of mercaptans being continuously subjected to the first treatment.

10. A 'process for converting a tertiary alkyl mercaptan of high molecular weight to a disul-A dewhich comprises contacting said mercaptan i in a first treatment with cupric chloride solution excess of approximately 174, which comprises l subjecting said mixture of mercapians to the action of an aqueous solution of cupricchloride` in liquid phase until a substantial` proportion of the mercaptans has been partially oxidized, and.

unoxidized mercaptans and copper compounds is obtained. i

, mercaptide, separating from the eiiiuent of said to effect a substantial conversion of said mercaptan to a disulfide and a cuprous mercaptide, separating from thefellluent of said first treatment an oil phase containing said disulfide and cuprous first treatment an vaqueous `phase consisting of a partially reduced aqueous 'copper solution containing hydrochloric acid and having a lower cupric copper content than the original cupric chloride solution, contacting said effluent aqueous phase with an, oxygen-containing gas to effect regeneration thereof and convert cuprous copper' contained therein""to cupric copper, commingling` said `eilluent oilfphase from said rst REFERENCES Vorrlm The following references are of record in the le of this patent:

4 12 nNrrED sTA'rEs PATENTS Number Name Date 2,042,053 Hoover May'26, 1936 2,094,485 Buell Sept. 28, 1937 2,149,035 Fuchs Feb. 28, 1939 1,951,324 Boslng Mar. 13, 1934 1,840,269 Borgstrom Jan. 5, 1932 .OTHER REFERENCES Ritter et a1., .r. Am. chem. soa,"- vol. 59, pp. 1251351, 23521937. 

